U.S. patent number 7,718,322 [Application Number 10/924,248] was granted by the patent office on 2010-05-18 for electrolyte for rechargeable lithium battery and rechargeable lithium battery comprising same.
This patent grant is currently assigned to Samsung SDI Co., Ltd.. Invention is credited to Tae-Shik Earmme, Kwang-Sup Kim, You-Mee Kim, Yong-Beom Lee, Eui-Hwan Song.
United States Patent |
7,718,322 |
Lee , et al. |
May 18, 2010 |
**Please see images for:
( Certificate of Correction ) ** |
Electrolyte for rechargeable lithium battery and rechargeable
lithium battery comprising same
Abstract
Disclosed in an electrolyte for a rechargeable lithium battery,
including a mixture of organic solvents including a cyclic solvent
and a nitrile-based solvent represented by formula 1 and a lithium
salt.
Inventors: |
Lee; Yong-Beom (Suwon-si,
KR), Song; Eui-Hwan (Suwon-si, KR), Kim;
Kwang-Sup (Suwon-si, KR), Earmme; Tae-Shik
(Suwon-si, KR), Kim; You-Mee (Suwon-si,
KR) |
Assignee: |
Samsung SDI Co., Ltd.
(Suwon-si, KR)
|
Family
ID: |
34067488 |
Appl.
No.: |
10/924,248 |
Filed: |
August 20, 2004 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20050084765 A1 |
Apr 21, 2005 |
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Foreign Application Priority Data
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Aug 20, 2003 [KR] |
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10-2003-0057716 |
Jan 29, 2004 [KR] |
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10-2004-0005874 |
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Current U.S.
Class: |
429/339; 429/338;
429/330; 429/329; 429/326; 429/324; 429/306; 429/231.95 |
Current CPC
Class: |
H01M
10/0569 (20130101); H01M 4/366 (20130101); H01M
10/0565 (20130101); H01M 10/0567 (20130101); H01M
10/0525 (20130101); H01M 4/525 (20130101); H01M
10/0587 (20130101); H01M 4/485 (20130101); H01M
2300/0082 (20130101); Y02E 60/10 (20130101); H01M
2300/004 (20130101); H01M 4/505 (20130101); H01M
4/131 (20130101) |
Current International
Class: |
H01M
6/16 (20060101) |
References Cited
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WO |
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WO 2004/023577 |
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Mar 2004 |
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WO |
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Primary Examiner: Yuan; Dah-Wei
Assistant Examiner: Martin; Angela J
Attorney, Agent or Firm: Christie, Parker & Hale,
LLP
Claims
What is claimed is:
1. An electrolyte for a rechargeable lithium battery comprising: a
lithium salt; a non-aqueous organic solvent comprising 70 to 95
volume % of an ester-based solvent comprising a cyclic ester; and 5
to 30 volume % of a nitrile-based solvent represented by the
formula: R--C.ident.N where R is selected from the group consisting
of C.sub.1 to C.sub.10 aliphatic hydrocarbons, C.sub.1 to C.sub.10
halogenated aliphatic hydrocarbons, C.sub.6 to C.sub.10 aromatic
hydrocarbons, and C.sub.6 to C.sub.10 halogenated aromatic
hydrocarbons.
2. The electrolyte of claim 1, wherein the non-aqueous organic
solvent includes 75 to 90 volume % of the ester-based solvent
comprising the cyclic ester and 10 to 25 volume % of the
nitrile-based solvent.
3. The electrolyte of claim 1, wherein the cyclic ester includes 10
to 40 volume % of ethylene carbonate, and 30 to 85 volume % of a
solvent selected from the group consisting of propylene carbonate,
butylene carbonate, .gamma.-butyrolactone, .gamma.-valerolactone,
.gamma.-caprolactone, .delta.-valerolactone, .di-elect
cons.-caprolactone, and mixtures thereof, and wherein the cyclic
ester is present in an amount from 70 to 95 volume %.
4. The electrolyte of claim 1, wherein the cyclic ester includes 10
to 15 volume % of ethylene carbonate, and 55 to 85 volume % of a
solvent selected from the group consisting of propylene carbonate,
butylene carbonate, .gamma.-butyrolactone, .gamma.-valerolactone,
.gamma.-caprolactone, .delta.-valerolactone, .di-elect
cons.-caprolactone, and mixtures thereof, and wherein the cyclic
ester is present in an amount from 70 to 95 volume %.
5. The electrolyte of claim 1, wherein R is selected from the group
consisting of C.sub.3 to C.sub.8 aliphatic hydrocarbons and C.sub.3
to C.sub.8 halogenated aliphatic hydrocarbons.
6. The electrolyte of claim 1, wherein the nitrile-based solvent is
selected from the group consisting of acetonitrile, propionitrile,
butyronitrile, t-butyl cyanide, valeronitrile, caprylonitrile,
heptyl cyanide, heptanenitrile, cyclopentane carbonitrile,
cyclohexane carbonitrile, 2-fluorobenzonitrile,
4-fluorobenzonitrile, difluorobenzonitrile, trifluorobenzonitrile,
2-chlorobenzonitrile, 4-chlorobenzonitrile, dichlorobenzonitrile,
trichlorobenzonitrile, 2-chloro-4-fluorobenzonitrile,
4-chloro-2-fluorobenzonitrile, phenylacetonitrile,
2-fluorophenylacetonitrile, and 4-fluorophenylacetonitrile.
7. The electrolyte of claim 1, wherein the organic solvent further
comprises a linear ester in an amount up to 70 parts by volume
based on 100 parts by volume of the total cyclic ester and the
nitrile-based solvent.
8. The electrolyte of claim 7, wherein the linear ester is selected
from the group consisting of dimethyl carbonate, ethylmethyl
carbonate, diethyl carbonate, dipropyl carbonate, dibutyl
carbonate, methyl acetate, ethyl acetate, methyl hexanoate, methyl
formate, and mixtures thereof.
9. The electrolyte of claim 1, wherein the electrolyte includes a
monomer and a polymerization initiator.
10. The electrolyte of claim 9, wherein the monomer is a first
monomer, wherein the electrolyte further includes a second monomer,
wherein: the first monomer has at least two functional groups at a
terminal end thereof, one functional group being selected from the
group consisting of unsaturated groups represented by formulas 2 to
4, and the first monomer has a molecular weight from 50 to 100,000;
and the second monomer has one functional group selected from the
group consisting of an unsaturated bond represented by formulas 2
to 4, and the second monomer has a molecular weight from 50 to
100,000; (R.sub.1)(R.sub.2)C.dbd.C(R.sub.3)--C(.dbd.O)-- (2)
(R.sub.1)(R.sub.2)C.dbd.C(R.sub.3)-- (3)
(R.sub.1)(R.sub.2)C.dbd.C(R.sub.3)--CH.sub.2-- (4) where R.sub.1,
R.sub.2 and R.sub.3 are the same or are independently selected from
the group consisting of H, C.sub.2 to C.sub.10 aliphatic or
aromatic hydrocarbons, --C.ident.N, and --OR.sub.5, where R.sub.5
is selected from the group consisting of H, CH.sub.3,
C.sub.2H.sub.5, --F, --Cl, and Br.
11. The electrolyte of claim 9, wherein the polymer electrolyte
includes from 0.01 to 20 wt % of monomer.
12. The electrolyte of claim 9, wherein the polymerization
initiator is an organic peroxide or an azo-based compound.
13. The electrolyte of claim 12, wherein the polymerization
initiator is selected from the group consisting of peroxy
dicarbonates selected from the group consisting of
di(4-t-butylcyclohexyl)peroxydicarbonate, di-2-ethylhexyl peroxy
dicarbonate, di-isopropyl peroxydicarbonate, di-3-methoxy butyl
peroxy dicarbonate, t-butyl peroxy isopropyl carbonate, t-butyl
peroxy 2-ethylhexyl carbonate, 1,6-bis(t-butyl
peroxycarbonyloxy)hexane, and diethylene glycol-bis(t-butyl peroxy
carbonate); diacyl peroxides selected from the group consisting of
diacetyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, and
bis-3,5,5-trimethyl hexanoyl peroxide; and peroxy esters selected
from the group consisting of t-butyl peroxypivalate, t-amyl peroxy
pivalate, t-butyl peroxy-2-ethyl hexanoate, t-hexylperoxy pivalate,
t-butyl peroxy neodecanoate, t-butyl peroxy neoheptanoate,
t-hexylperoxy pivalate, 1,1,3,3-tetramethylbutyl peroxy
neodecanoate, 1,1,3,3-tetramethyl butyl 2-ethylhexanoate,
t-amylperoxy 2-ethyl hexanoate, t-butyl peroxy isobutyrate,
t-amylperoxy 3,5,5-trimethyl hexanoyl, t-butyl peroxy isobutyrate,
t-amylperoxy 3,5,5-trimethyl hexanoyl, t-butyl peroxy
3,5,5-trimethyl hexanoate, t-butyl peroxy acetate, t-butyl peroxy
benzoate, and di-butylperoxy trimethyl adipate; and azo-based
compounds selected from the group consisting of
2,2'-azo-bis(2,4-dimethylvaleronitrile) and
1,1'-azo-bis(cyanocyclo-hexane).
14. The electrolyte of claim 1, wherein the lithium salt is
selected from the group consisting of LiPF.sub.6, LiBF.sub.4,
LiSbF.sub.6, LiAsF.sub.6, LiClO.sub.4, LiCF.sub.3SO.sub.3,
LiN(CF.sub.3SO.sub.2).sub.2, LiN(C.sub.2F.sub.5SO.sub.2).sub.2,
LiAlO.sub.4, LiAlCl.sub.4,
LiN(C.sub.xF.sub.2x+1SO.sub.2)(C.sub.yF.sub.2y+1SO.sub.2) where x
and y are natural numbers, LiSO.sub.3CF.sub.3, and mixtures
thereof.
15. The electrolyte of claim 1, wherein the electrolyte further
comprises an additive selected from the group consisting of a
substituted carbonate with a substitution group, vinylene
carbonate, divinyl sulfone, ethylene sulfite, and mixtures thereof,
wherein the substitution group is selected from the group
consisting of halogens, a cyano (CN) and a nitro (NO.sub.2).
16. The electrolyte of claim 15, wherein the additive is a
substituted carbonate with a substitution group selected from the
group consisting of halogens, a cyano (CN) and a nitro
(NO.sub.2).
17. The electrolyte of claim 16, wherein the substituted carbonate
is represented by the formula: ##STR00002## where X is selected
from the group consisting of halogens, cyano (CN) and nitro
(NO.sub.2).
18. The electrolyte of claim 17, wherein the substituted carbonate
is fluoroethylene carbonate.
19. The electrolyte of claim 16, wherein the additive is present in
an amount between 0.01 and 10 parts by weight based on 100 parts by
weight of the total electrolyte.
20. A rechargeable lithium battery comprising: a positive electrode
comprising a positive active material in which lithium
intercalation reversibly occurs; a negative electrode comprising a
negative active material in which lithium intercalation reversibly
occurs; an electrolyte comprising an organic solvent and a lithium
salt, the organic solvent comprising 70 to 95 volume % of an
ester-based solvent comprising a cyclic ester and 5 to 30 volume %
of a nitrile-based solvent represented by the formula: R--C.ident.N
where R is selected from the group consisting of C.sub.1 to
C.sub.10 aliphatic hydrocarbons, C.sub.1 to C.sub.10 halogenated
aliphatic hydrocarbons, C.sub.6 to C.sub.10 aromatic hydrocarbons,
and C.sub.6 to C.sub.10 halogenated aliphatic hydrocarbons.
21. The rechargeable lithium battery of claim 20, wherein the
non-aqueous organic solvent includes 75 to 90 volume % of the
ester-based solvent comprising the cyclic ester and 10 to 25 volume
% of the nitrile-based solvent.
22. The rechargeable lithium battery of claim 20, wherein the
cyclic ester includes 10 to 40 volume % of ethylene carbonate, and
30 to 85 volume % of a solvent selected from the group consisting
of propylene carbonate, butylene carbonate, .gamma.-butyrolactone,
.gamma.-valerolactone, .gamma.-caprolactone, .delta.-valerolactone,
and .di-elect cons.-caprolactone, and wherein the cyclic ester is
present in an amount from 70 to 95 volume %.
23. The rechargeable lithium battery of claim 20, wherein the
cyclic ester includes 10 to 15 volume % of ethylene carbonate, and
55 to 85 volume % of a solvent selected from the group consisting
of propylene carbonate, butylene carbonate, .gamma.-butyrolactone,
.gamma.-valerolactone, .gamma.-caprolactone, .delta.-valerolactone,
.di-elect cons.-caprolactone, and mixtures thereof, and wherein the
cyclic ester is present in an amount from 70 to 95 volume %.
24. The rechargeable lithium battery of claim 20, wherein R is
selected from the group consisting of C.sub.3 to C.sub.8 aliphatic
hydrocarbons and C.sub.3 to C.sub.8 halogenated aliphatic
hydrocarbons.
25. The rechargeable lithium battery of claim 20, wherein the
nitrile-based solvent is selected from the group consisting of
acetonitrile, propionitrile, butyronitrile, t-butyl cyanide,
valeronitrile, caprylonitrile, heptyl cyanide, heptanenitrile,
cyclopentane carbonitrile, cyclohexane carbonitrile,
2-fluorobenzonitrile, 4-fluorobenzonitrile, difluorobenzonitrile,
trifluorobenzonitrile, 2-chlorobenzonitrile, 4-chlorobenzonitrile,
dichlorobenzonitrile, trichlorobenzonitrile,
2-chloro-4-fluorobenzonitrile, 4-chloro-2-fluorobenzonitrile,
phenylacetonitrile, 2-fluorophenylacetonitrile,
4-fluorophenylacetonitrile and mixtures thereof.
26. The rechargeable lithium battery of claim 20, wherein the
organic solvent further comprises a linear ester in an amount up to
70 parts by volume based on 100 parts by volume of the total cyclic
ester and the nitrile-based solvent.
27. The rechargeable lithium battery of claim 20, wherein the
electrolyte further includes a monomer and a polymerization
initiator.
28. The rechargeable lithium battery of claim 27, wherein the
monomer is a first monomer, wherein the electrolyte further
includes a second monomer, wherein: the first monomer has at least
two functional groups at a terminal end thereof, one functional
group being selected from the group consisting of unsaturated
groups represented by formulas 2 to 4, and the first monomer has a
molecular weight from 100 to 10,000; and the second monomer has one
functional group selected from the group consisting of unsaturated
bonds represented by formulas 2 to 4, and the second monomer has a
molecular weight from 100 to 10,000:
(R.sub.1)(R.sub.2)C.dbd.C(R.sub.3)--C(.dbd.O)-- (2)
(R.sub.1)(R.sub.2)C.dbd.C(R.sub.3)-- (3)
(R.sub.1)(R.sub.2)C.dbd.C(R.sub.3)--CH.sub.2-- (4) where, R.sub.1,
R.sub.2 and R.sub.3 are the same or are independently selected from
the group consisting of H, C.sub.2 to C.sub.10 aliphatic or
aromatic hydrocarbons, --C.ident.N, and --OR.sub.5, where R.sub.5
is selected from the group consisting of H, CH.sub.3,
C.sub.2H.sub.5, --F, --Cl and Br.
29. The rechargeable lithium battery of claim 27, wherein the
polymerization initiator is an organic peroxide or an azo-based
compound.
30. The rechargeable lithium battery of claim 29, wherein the
polymerization initiator is selected from the group consisting of
peroxy dicarbonates selected from the group consisting of
di(4-t-butylcyclohexyl)peroxydicarbonate, di-2-ethylhexyl peroxy
dicarbonate, di-isopropyl peroxydicarbonate, di-3-methoxy butyl
peroxy dicarbonate, t-butyl peroxy isopropyl carbonate, t-butyl
peroxy 2-ethylhexyl carbonate, 1,6-bis(t-butyl
peroxycarbonyloxy)hexane, and diethylene glycol-bis(t-butyl peroxy
carbonate); diacyl peroxides selected from the group consisting of
diacetyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, and
bis-3,5,5-trimethyl hexanoyl peroxide; peroxyesters selected from
the group consisting of t-butyl peroxy pivalate, t-amyl
peroxypivalate, t-butyl peroxy-2-ethyl hexanoate, t-hexylperoxy
pivalate, t-butyl peroxy neodecanoate, t-butyl peroxy
neoheptanoate, t-hexylperoxy pivalate, 1,1,3,3-tetramethylbutyl
peroxy neodecanoate, 1,1,3,3-tetramethyl butyl 2-ethylhexanoate,
t-amylperoxy 2-ethyl hexanoate, t-butyl peroxy isobutyrate,
t-amylperoxy 3,5,5-trimethyl hexanoyl, t-butyl peroxy isobutyrate,
t-amylperoxy 3,5,5-trimethyl hexanoyl, t-butyl peroxy
3,5,5-trimethyl hexanoate, t-butyl peroxy acetate, t-butyl peroxy
benzoate, and di-butylperoxy trimethyl adipate; and azo-based
compounds selected from the group consisting of
2,2'-azo-bis(2,4-dimethylvaleronitrile) and
1,1'-azo-bis(cyanocyclo-hexane).
31. The rechargeable lithium battery of claim 20, wherein the
lithium salt is selected from the group consisting of LiPF.sub.6,
LiBF.sub.4, LiSbF.sub.6, LiAsF.sub.6, LiClO.sub.4,
LiCF.sub.3SO.sub.3, LiN(CF.sub.3SO.sub.2).sub.2,
LiN(C.sub.2F.sub.5SO.sub.2).sub.2, LiAlO.sub.4, LiAlCl.sub.4,
LiN(C.sub.xF.sub.2x+1SO.sub.2)(C.sub.yF.sub.2y+1SO.sub.2) where, x
and y are natural numbers, LiSO.sub.3CF.sub.3, and mixtures
thereof.
32. The rechargeable lithium battery of claim 20, wherein the
electrolyte further comprises an additive selected from the group
consisting of a substituted carbonate with a substitution group,
vinylene carbonate, divinyl sulfone, ethylene sulfite, and
combinations thereof, wherein the substitution group is selected
from the group consisting of halogens, a cyano (CN) and a nitro
(NO.sub.2).
33. The rechargeable lithium battery of claim 32, wherein the
additive is a substituted carbonate with a substitution group
selected from the group consisting of halogens, a cyano (CN) and a
nitro (NO.sub.2).
34. The rechargeable lithium battery of claim 33, wherein the
substituted carbonate is represented by the formula: ##STR00003##
where X is selected from the group consisting of halogens, cyano
(CN) and nitro (NO.sub.2).
35. The rechargeable lithium battery of claim 34, wherein the
substituted carbonate is fluoroethylene carbonate.
36. The rechargeable lithium battery of claim 20, wherein the
positive active material is a nickel-based compound.
37. The rechargeable lithium battery of claim 36, wherein the
positive active material is a nickel-based compound represented by
formulas 6 or 7: Li.sub.xNi.sub.yM.sub.1-yA.sub.2 (6)
Li.sub.xNi.sub.yM.sub.1-yO.sub.2-zX.sub.z (7) where
0.90.ltoreq.x.ltoreq.1.1, 0.1.ltoreq.y.ltoreq.0.9, and
0.ltoreq.z.ltoreq.0.5; M is selected from the group consisting of
Al, Ni, Go, Mn, Cr, Fe, Mg, Sr, V, rare earth elements and
combinations thereof; A is selected from O, F, S or P; and X is F,
S or P.
38. The rechargeable lithium battery of claim 20, wherein the
positive active material is a nickel-based compound, or a mixture
of a nickel-based compound and, a cobalt-based compound or a
manganese-based compound.
39. An electrolyte for a rechargeable lithium battery comprising: a
non-aqueous organic solvent comprising 70 to 95 volume % of an
ester-based solvent comprising a cyclic ester comprising 10 to 40
volume % of ethylene carbonate and 5 to 30 volume % of a
nitrile-based solvent represented by formula (1); and a lithium
salt R--C.ident.N (1) where R is selected from the group consisting
of C.sub.1 to C.sub.10 aliphatic hydrocarbons, C.sub.1 to C.sub.10
halogenated aliphatic hydrocarbons, C.sub.6 to C.sub.10 aromatic
hydrocarbons, and C.sub.6 to C.sub.10 halogenated aromatic
hydrocarbons.
40. The electrolyte of claim 39, wherein the non-aqueous organic
solvent includes 75 to 90 volume % of the ester-based solvent
comprising the cyclic ester, and the nitrile-based solvent from 10
to 25 volume %.
41. The electrolyte of claim 39, wherein the cyclic ester includes
30 to 85 volume % of a solvent selected from the group consisting
of propylene carbonate, butylene carbonate, .gamma.-butyrolactone,
.gamma.-valerolactone, .gamma.-caprolactone, .delta.-valerolactone,
.di-elect cons.-caprolactone, and mixtures thereof, and wherein the
cyclic ester is present in an amount from 70 to 95 volume %.
42. The electrolyte of claim 41, wherein the cyclic ester includes
10 to 15 volume % of ethylene carbonate, and 55 to 85 volume % of a
solvent selected from the group consisting of propylene carbonate,
butylene carbonate, .gamma.-butyrolactone, .gamma.-valerolactone,
.gamma.-caprolactone, .delta.-valerolactone, .di-elect
cons.-caprolactone, and mixtures thereof, and wherein the cyclic
ester is present in an amount from 70 to 95 volume %.
43. The electrolyte of claim 39, wherein R is selected from the
group consisting of C.sub.3 to C.sub.8 aliphatic hydrocarbons and
C.sub.3 to C.sub.8 halogenated aliphatic hydrocarbons.
44. The electrolyte of claim 39, wherein the nitrile-based solvent
is selected from the group consisting of acetonitrile,
propionitrile, butyronitrile, t-butyl cyanide, valeronitrile,
caprylonitrile, heptyl cyanide, heptanenitrile, cyclopentane
carbonitrile, cyclohexane carbonitrile, 2-fluorobenzonitrile,
4-fluorobenzonitrile, difluorobenzonitrile, trifluorobenzonitrile,
2-chlorobenzonitrile, 4-chlorobenzonitrile, dichlorobenzonitrile,
trichlorobenzonitrile, 2-chloro-4-fluorobenzonitrile,
4-chloro-2-fluorobenzonitrile, phenylacetonitrile,
2-fluorophenylacetonitrile, and 4-fluorophenylacetonitrile.
45. The electrolyte of claim 39, wherein the organic solvent
further comprises a linear ester in an amount up to 70 parts by
volume based on 100 parts by volume of the total cyclic ester and
the nitrile-based solvent.
46. The electrolyte of claim 45, wherein the linear ester is
selected from the group consisting of dimethyl carbonate, ethyl
methyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl
carbonate, methyl acetate, ethyl acetate, methyl hexanoate, methyl
formate, and mixtures thereof.
47. The electrolyte of claim 38, wherein the electrolyte further
includes a monomer and a polymerization initiator.
48. The electrolyte of claim 47, wherein the monomer is a first
monomer and the electrolyte further includes a second monomer,
wherein: the first monomer has at least two functional groups at a
terminal end thereof, one functional group selected from the group
consisting of unsaturated groups represented by formulas 2 to 4,
and the first monomer has a molecular weight from 100 to 10,000;
and the second monomer has one functional group selected from the
group consisting of an unsaturated bond represented by formulas 2
to 4, and the second monomer has a molecular weight from 100 to
10,000: (R.sub.1)(R.sub.2)C.dbd.C(R.sub.3)--C(.dbd.O)-- (2)
(R.sub.1)(R.sub.2)C.dbd.C(R.sub.3)-- (3)
(R.sub.1)(R.sub.2)C.dbd.C(R.sub.3)--CH.sub.2-- (4) where, R.sub.1,
R.sub.2 and R.sub.3 are the same or are independently selected from
the group consisting of H, C.sub.2 to C.sub.10 aliphatic and
aromatic hydrocarbons, --C.ident.N, and --OR.sub.5, where R.sub.5
is selected from the group consisting of H, CH.sub.3,
C.sub.2H.sub.5, --F, --Cl and Br.
49. The electrolyte of claim 47, wherein the polymer electrolyte
includes 0.01 to 20 wt % of the monomer.
50. The electrolyte of claim 47, wherein the polymerization
initiator is an organic peroxide or an azo-based compound.
51. The electrolyte of claim 50, wherein the polymerization
initiator is selected from the group consisting of peroxy
dicarbonates selected from the group consisting of
di(4-t-butylcyclohexyl)peroxydicarbonate, di-2-ethylhexyl peroxy
dicarbonate, di-isopropyl peroxydicarbonate, di-3-methoxy butyl
peroxy dicarbonate, t-butyl peroxy isopropyl carbonate, t-butyl
peroxy 2-ethylhexyl carbonate, 1,6-bis(t-butyl
peroxycarbonyloxy)hexane, and diethylene glycol-bis(t-butyl peroxy
carbonate); diacyl peroxides selected from the group consisting of
diacetyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, and
bis-3,5,5-trimethyl hexanoyl peroxide; peroxyesters selected from
the group consisting of t-butyl peroxy pivalate, t-amyl
peroxypivalate, t-butyl peroxy-2-ethyl hexanoate, t-hexylperoxy
pivalate, t-butyl peroxy neodecanoate, t-butyl peroxy
neoheptanoate, t-hexylperoxy pivalate, 1,1,3,3-tetramethylbutyl
peroxy neodecanoate, 1,1,3,3-tetramethyl butyl 2-ethylhexanoate,
t-amylperoxy 2-ethyl hexanoate, t-butyl peroxy isobutyrate,
t-amylperoxy 3,5,5-trimethyl hexanoyl, t-butyl peroxy isobutyrate,
t-amylperoxy 3,5,5-trimethyl hexanoyl, t-butyl peroxy
3,5,5-trimethyl hexanoate, t-butyl peroxy acetate, t-butyl peroxy
benzoate, and di-butylperoxy trimethyl adipate; and azo-based
compounds selected from the group consisting of
2,2'-azo-bis(2,4-dimethylvaleronitrile) and
1,1'-azo-bis(cyanocyclo-hexane).
52. The electrolyte of claim 39, wherein the lithium salt is
selected from the group consisting of LiPF.sub.6, LiBF.sub.4,
LiSbF.sub.6, LiAsF.sub.6, LiClO.sub.4, LiCF.sub.3SO.sub.3,
LiN(CF.sub.3SO.sub.2).sub.2, LiN(C.sub.2F.sub.5SO.sub.2).sub.2,
LiAlO.sub.4, LiAlCl.sub.4,
LiN(C.sub.xF.sub.2x+1SO.sub.2)(C.sub.yF.sub.2y+1SO.sub.2) where, x
and y are natural numbers, LiSO.sub.3CF.sub.3, and mixtures
thereof.
53. The electrolyte of claim 39, wherein the electrolyte further
comprises an additive selected from the group consisting of a
substituted carbonate with a substitution group, vinylene
carbonate, divinyl sulfone, ethylene sulfite, and combinations
thereof, wherein the substitution group is selected from the group
consisting of halogens, a cyano (CN) and a nitro (NO.sub.2).
54. The electrolyte of claim 52, wherein the additive is a
substituted carbonate with a substitution group selected from the
group consisting of halogens, a cyano (CN) and a nitro
(NO.sub.2).
55. The electrolyte of claim 54, wherein the substituted carbonate
is represented by the formula: ##STR00004## where X is selected
from the group consisting of halogens, cyano (CN) and nitro
(NO.sub.2).
56. The electrolyte of claim 55, wherein the substituted carbonate
is fluoroethylene carbonate.
57. The electrolyte of claim 54, wherein the additive is present in
an amount between 0.01 and 10 parts by weight based on 100 parts by
weight of the total electrolyte.
58. A rechargeable lithium battery comprising: a positive electrode
comprising a Nickel-based positive active material; a negative
electrode comprising a negative active material in which lithium
intercalation reversibly occurs; an electrolyte comprising an
organic solvent and a lithium salt, the organic solvent comprising
70 to 95 volume % of an ester-based solvent comprising a cyclic
ester and 5 to 30 volume % of a nitrile-based solvent represented
by the formula: R--C.ident.N where R is selected from the group
consisting of C.sub.1 to C.sub.10 aliphatic hydrocarbons, C.sub.1
to C.sub.10 halogenated aliphatic hydrocarbons, C.sub.6 to C.sub.10
aromatic hydrocarbons, and C.sub.6 to C.sub.10 halogenated
aliphatic hydrocarbons.
59. The rechargeable lithium battery of claim 58, wherein the
non-aqueous organic solvent includes 75 to 90 volume % of the
ester-based solvent comprising the cyclic ester and 10 to 25 volume
% of the nitrile-based solvent.
60. The rechargeable lithium battery of claim 58, wherein the
cyclic ester includes 10 to 40 volume % of ethylene carbonate, and
30 to 85 volume % of a solvent selected from the group consisting
of propylene carbonate, butylene carbonate, .gamma.-butyrolactone,
.gamma.-valerolactone, .gamma.-caprolactone, .delta.-valerolactone,
.di-elect cons.-caprolactone, and mixtures thereof, and wherein the
cyclic ester is present in a total amount of 70 to 95 volume %.
61. The rechargeable lithium battery of claim 60, wherein the
cyclic ester includes 10 to 15 volume % of ethylene carbonate, and
55 to 85 volume % of a solvent selected from the group consisting
of propylene carbonate, butylene carbonate, .gamma.-butyrolactone,
.gamma.-valerolactone, .gamma.-caprolactone, .delta.-valerolactone,
.di-elect cons.-caprolactone, and mixtures thereof, and wherein the
cyclic ester is present in a total amount of 70 to 95 volume %.
62. The rechargeable lithium battery of claim 58, wherein R is
selected from the group consisting of C.sub.3 to C.sub.8 aliphatic
hydrocarbons and C.sub.3 to C.sub.8 halogenated aliphatic
hydrocarbons.
63. The rechargeable lithium battery of claim 58, wherein the
nitrile-based solvent is selected from the group consisting of
acetonitrile, propionitrile, butyronitrile, t-butyl cyanide,
valeronitrile, caprylonitrile, heptyl cyanide, heptanenitrile,
cyclopentane carbonitrile, cyclohexane carbonitrile,
2-fluorobenzonitrile, 4-fluorobenzonitrile, difluorobenzonitrile,
trifluorobenzonitrile, 2-chlorobenzonitrile, 4-chlorobenzonitrile,
dichlorobenzonitrile, trichlorobenzonitrile,
2-chloro-4-fluorobenzonitrile, 4-chloro-2-fluorobenzonitrile,
phenylacetonitrile, 2-fluorophenylacetonitrile,
4-fluorophenylacetonitrile and mixtures thereof.
64. The rechargeable lithium battery of claim 58, wherein the
organic solvent further comprises a linear ester in an amount up to
70 parts by volume based on 100 parts by volume of the total cyclic
ester and the nitrile-based solvent.
65. The rechargeable lithium battery of claim 58, wherein the
electrolyte further includes a monomer and a polymerization
initiator.
66. The rechargeable lithium battery of claim 65, wherein the
monomer is a first monomer and the electrolyte further includes a
second monomer, wherein: the first monomer has at least two
functional groups at a terminal end thereof, one functional group
selected from the group consisting of unsaturated groups
represented by formulas 2 to 4, and the first monomer has a
molecular weight from 100 to 10,000; and the second monomer has one
functional group selected from the group consisting of unsaturated
bond represented by formulas 2 to 4, and the second monomer has a
molecular weight from 100 to 10,000:
(R.sub.1)(R.sub.2)C.dbd.C(R.sub.3)--C(.dbd.O)-- (2)
(R.sub.1)(R.sub.2)C.dbd.C(R.sub.3)-- (3)
(R.sub.1)(R.sub.2)C.dbd.C(R.sub.3)--CH.sub.2-- (4) where, R.sub.1,
R.sub.2 and R.sub.3 are the same or are independently selected from
the group consisting of H, C.sub.2 to C.sub.10 aliphatic or
aromatic hydrocarbons, --C.ident.N, and --OR.sub.5, where R.sub.5
is selected from the group consisting of H, CH.sub.3,
C.sub.2H.sub.5, --F, --Cl and Br.
67. The rechargeable lithium battery of claim 58, wherein the
polymerization initiator is an organic peroxide or an azo-based
compound.
68. The rechargeable lithium battery of claim 67, wherein the
polymerization initiator is selected from the group consisting of
peroxy dicarbonates selected from the group consisting of
di(4-t-butylcyclohexyl)peroxydicarbonate, di-2-ethylhexyl peroxy
dicarbonate, di-isopropyl peroxydicarbonate, di-3-methoxy butyl
peroxy dicarbonate, t-butyl peroxy isopropyl carbonate, t-butyl
peroxy 2-ethylhexyl carbonate, 1,6-bis(t-butyl
peroxycarbonyloxy)hexane, and diethylene glycol-bis(t-butyl peroxy
carbonate); diacyl peroxides selected from the group consisting of
diacetyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, and
bis-3,5,5-trimethyl hexanoyl peroxide; peroxyesters selected from
the group consisting of t-butyl peroxy pivalate, t-amyl
peroxypivalate, t-butyl peroxy-2-ethyl hexanoate, t-hexylperoxy
pivalate, t-butyl peroxy neodecanoate, t-butyl peroxy
neoheptanoate, t-hexylperoxy pivalate, 1,1,3,3-tetramethylbutyl
peroxy neodecanoate, 1,1,3,3-tetramethyl butyl 2-ethylhexanoate,
t-amylperoxy 2-ethyl hexanoate, t-butyl peroxy isobutyrate,
t-amylperoxy 3,5,5-trimethyl hexanoyl, t-butyl peroxy isobutyrate,
t-amylperoxy 3,5,5-trimethyl hexanoyl, t-butyl peroxy
3,5,5-trimethyl hexanoate, t-butyl peroxy acetate, t-butyl peroxy
benzoate, and di-butylperoxy trimethyl adipate; and azo-based
compounds selected from the group consisting of
2,2'-azo-bis(2,4-dimethylvaleronitrile) and
1,1'-azo-bis(cyanocyclo-hexane).
69. The rechargeable lithium battery of claim 58, wherein the
lithium salt is selected from the group consisting of LiPF.sub.6,
LiBF.sub.4, LiSbF.sub.6, LiAsF.sub.6, LiClO.sub.4,
LiCF.sub.3SO.sub.3, LiN(CF.sub.3SO.sub.2).sub.2,
LiN(C.sub.2F.sub.5SO.sub.2).sub.2, LiAlO.sub.4, LiAlCl.sub.4,
LiN(C.sub.xF.sub.2x+1SO.sub.2)(C.sub.yF.sub.2y+1SO.sub.2) where, x
and y are natural numbers, LiSO.sub.3CF.sub.3, and mixtures
thereof.
70. The rechargeable lithium battery of claim 58, wherein the
electrolyte further comprises an additive selected from the group
consisting of a substituted carbonate with a substitution group,
vinylene carbonate, divinyl sulfone, ethylene sulfite, and
combinations thereof, wherein the substitution group is selected
from the group consisting of halogens, a cyano (CN) and a nitro
(NO.sub.2).
71. The rechargeable lithium battery of claim 70, wherein the
substituted carbonate is represented by the formula: ##STR00005##
where X is selected from the group consisting of halogens, cyano
(CN) and nitro (NO.sub.2).
72. The rechargeable lithium battery of claim 71, wherein the
substituted carbonate is fluoroethylene carbonate.
73. The rechargeable lithium battery of claim 58, wherein the
positive active material is a nickel-based compound represented by
formulas 6 or 7: Li.sub.xNi.sub.yM.sub.1-yA.sub.2 (6)
Li.sub.xNi.sub.yM.sub.1-yO.sub.2-zX.sub.z (7) where
0.90.ltoreq.x.ltoreq.1.1, 0.1.ltoreq.y.ltoreq.0.9, and
0.ltoreq.z.ltoreq.0.5; M is selected from the group consisting of
Al, Ni, Go, Mn, Cr, Fe, Mg, Sr, V, rare earth elements and
combinations thereof; A is selected from the group consisting of O,
F, S and P; and X is F, S or P.
Description
CROSS REFERENCE TO RELATED APPLICATION
This application is based on and claims priority of Korean Patent
Application Nos. 2003-57716 and 2004-5874 filed in the Korean
Intellectual Property Office on Aug. 20, 2003 and Jan. 29, 2004,
respectively, the entire disclosures of which are incorporated
hereinto by reference.
FIELD OF THE INVENTION
The present invention relates to an electrolyte for a rechargeable
lithium battery and a rechargeable lithium battery comprising the
same, and more particularly, to an electrolyte for a rechargeable
lithium battery exhibiting improved storage characteristics and
suppression of swelling at high temperatures, and a rechargeable
lithium battery comprising the same.
BACKGROUND OF THE INVENTION
Recently, the rapid development of smaller, lighter, and higher
performance electronic and communication equipment has required the
development of high performance and large capacity batteries to
power such equipment. The demands for large capacity batteries have
led to investigations into rechargeable lithium batteries. Positive
active materials for rechargeable lithium batteries generally use
lithium-transition metal oxides, and negative active materials
generally use crystalline or amorphous carbonaceous materials or
carbon composites. The active materials are coated on a current
collector with a predetermined thickness and length, or they are
formed as a film to produce electrodes. The electrodes together
with a separator are wound to produce an electrode element, and the
electrode element is inserted into a battery case such as a can
followed by insertion of an electrolyte to fabricate a battery.
The electrolyte includes lithium salts and organic solvents. The
organic solvents may be mixed solvents of between two and five
components of cyclic carbonates such as ethylene carbonate or
propylene carbonate, or linear carbonates such as dimethyl
carbonate, ethylmethyl carbonate, or diethyl carbonate. However,
these solvents are known to severely expand at high temperatures,
causing a swelling phenomenon. The swelling phenomenon is partly
manifested in a battery by gas generated due to decomposition of
the electrolyte at high temperatures in the battery.
Such a swelling phenomenon can be reduced in lithium polymer
batteries compared to lithium ion batteries. However, the use of a
polymer electrolyte with a nickel-based positive active material
(e.g. LiNiMO.sub.2, where M is selected from Co, Mn, Al, P, Fe or
Mg) has generally been ineffective.
Several attempts to use solvents with a high boiling point and a
high dielectric constant, such as .gamma.-butyrolactone, have been
promising. Conventionally, the high dielectric constant solvent is
generally used together with ethylene carbonate, which results in
an extremely high viscosity with poor wettability of the separator.
In another attempt, solvents with low boiling points and low
dielectric constants have been used. However, these attempts still
have problems associated with high swelling (Japanese Patent
Laid-Open No. 2000-235868, U.S. Pat. Nos. 5,079,109, 5,272,022,
5,552,243, 5,521,027, 6,117,596, and 5,851,693, and "New thin
lithium-ion batteries using a liquid electrolyte with thermal
stability" Journal of power sources, 97-98, 677-680(2001), Notio
Takami et al.)
Other attempts to inhibit the swelling phenomenon are in U.S. Pat.
No. 4,830,939 disclosing a liquid electrolyte containing a
polyethylenically unsaturated monomeric material or a prepolymeric
material, and U.S. Pat. No. 4,866,716 disclosing a cross-linked
polyether which is a product of a vinyl-ether. In addition, U.S.
Pat. No. 4,970,012 discloses that a polymeric solid electrolyte
includes crosslinked molecules of a radiation-cured substance of a
cinnamate ester and polyethene oxide, and U.S. Pat. No. 4,908,283
discloses that a polymeric electrolyte includes a cured product of
an acryloyl-denaturated polyalkylene oxide.
Such a swelling phenomenon is especially severe in batteries with a
mixture of a lithium cobalt-based compound and a lithium
nickel-based compound which exhibits higher capacity than other
compounds.
SUMMARY OF THE INVENTION
In one embodiment of the invention an electrolyte is provided for a
rechargeable lithium battery which is capable of inhibiting
high-temperature swelling.
In another embodiment of the invention, a rechargeable lithium
battery is provided which includes the electrolyte.
These and other aspects may be achieved by an electrolyte for a
rechargeable lithium battery including a non-aqueous organic
solvent and a lithium salt. In one embodiment of the invention, the
non-aqueous organic solvent includes 70 to 95 volume % of an
ester-based solvent, the ester-based solvent including a cyclic
ester, and a nitrile-based solvent represented by formula 1 of 5 to
30 volume %: R--C.ident.N (1) where R is a C.sub.1 to C.sub.10
aliphatic hydrocarbon or halogenated aliphatic hydrocarbon, or a
C.sub.6 to C.sub.10 aromatic hydrocarbon or halogenated aromatic
hydrocarbon.
In yet another embodiment of the invention, a rechargeable lithium
battery is provided including the electrolyte, a positive electrode
and a negative electrode. The positive electrode and the negative
electrode include active material in which lithium intercalation
reversibly occurs. Preferably, the positive active material is a
nickel-included compound.
BRIEF DESCRIPTION OF THE DRAWINGS
A more complete appreciation of the invention, and many of the
attendant advantages thereof, will be readily apparent as the same
becomes better understood by reference to the following detailed
description when considered in conjunction with the accompanying
drawings, wherein:
FIG. 1 is a schematic view showing a rechargeable lithium battery
according to the present invention; and
FIG. 2 is a graph illustrating cycle life characteristics of the
cells according to Examples 7 to 10 of the present invention and
Comparative Example 1.
DETAILED DESCRIPTION
The present invention relates to an electrolyte including a
nitrile-based solvent for improving swelling and battery
performance. The electrolyte of the present invention includes
non-aqueous organic solvents and a lithium salt. The non-aqueous
organic solvents include an ester-based solvent including a cyclic
ester and a nitrile-based solvent.
The nitrile-based solvent is represented by formula 1: R--C.ident.N
(1)
where R is a C.sub.1 to C.sub.10 hydrocarbon or halogenated
hydrocarbon, preferably a C.sub.6 to C.sub.10 aromatic hydrocarbon
or halogenated aromatic hydrocarbon, or a C.sub.3 to C.sub.8
aliphatic hydrocarbon or halogenated aliphatic hydrocarbon, and
more preferably a C.sub.6 to C.sub.8 aliphatic hydrocarbon or
halogenated aliphatic hydrocarbon. Higher alkyl groups with a
higher number of carbons are preferred because they have increased
boiling points so that stability is improved, and the decomposition
on the aliphatic hydrocarbons rarely occurs compared to the
aromatic hydrocarbons. If the R is an unsaturated hydrocarbon, e.g.
methacrylate, it can be used as a solvent for an electrolyte.
Examples of the nitrile-based solvent include acetonitrile,
propionitrile, butyronitrile, t-butyl cyanide, valeronitrile,
caprylonitrile, heptyl cyanide, heptanenitrile, cyclopentane
carbonitrile, cyclohexane carbonitrile, 2-fluorobenzonitrile,
4-fluorobenzonitrile, difluorobenzonitrile, trifluorobenzonitrile,
2-chlorobenzonitrile, 4-chlorobenzonitrile, dichlorobenzonitrile,
trichlorobenzonitrile, 2-chloro-4-fluorobenzonitrile,
4-chloro-2-fluorobenzonitrile, phenylacetonitrile,
2-fluorophenylacetonitrile, and 4-fluoroacetonitrile.
A low viscosity and high dielectric constant of the nitrile-based
compound can repress the swelling phenomenon.
The nitrile-based solvent is preferably present in an amount from 5
to 30 volume %, and more preferably 15 to 25 volume %. An amount of
less than 5 volume % of the nitrile-based cannot achieve the
desired swelling inhibition. An amount of more than 30 volume %
deteriorates the battery performance. That is, the effect of the
present invention cannot be obtained from an amount of more than 30
volume %. It is expected that Japanese Patent Laid-Open No.
2000-124077 using 60 volume % or more of acetonitrile causes the
deterioration of the battery performance and problems associated
with safety. Such problems are also expected in U.S. Pat. No.
6,190,804 in which nitrile is only used as a solvent for preparing
a solid electrolyte, and where the amount of the nitrile used is
not disclosed.
The electrolyte of the present invention includes an ester-based
solvent including a cyclic ester in an amount of 70 to 95 volume %.
The cyclic ester preferably includes 10 to 40 volume % of ethylene
carbonate, and more preferably 10 to 15 volume % with respect to
the electrolyte. An amount of more than 40 volume % of the ethylene
carbonate cannot achieve the desired swelling inhibition. An amount
of less than 10 volume % deteriorates the battery performance.
Thus, it is expected that the effect of the use of the ethylene
carbonate of the present invention cannot be obtained from Japanese
Patent Laid-Open No. Hei. 7-320748 disclosing ethylene carbonate at
25 to 95 volume %.
The remaining amount, 30 to 85 volume %, and preferably 55 to 85
volume % with respect to the electrolyte, may be propylene
carbonate, butylene carbonate, .gamma.-butyrolactone,
.gamma.-valerolactone, .gamma.-caprolactone, .delta.-valerolactone,
.di-elect cons.-valerolactone, or a mixture thereof.
The electrolyte of the present invention may further include a
linear ester. The amount of the linear ester is preferably between
0 parts by volume and 70 parts by volume based on 100 parts by
volume of the total cyclic ester and the nitrile-based solvents. If
the amount of the linear ester is more than 70 parts by volume,
swelling occurs.
The linear ester preferably includes at least one compound selected
from dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate,
dipropyl carbonate, dibutyl carbonate, methyl acetate, ethyl
acetate, methyl hexanoate, methyl formate, and mixtures
thereof.
The electrolyte of the present invention may further include
carbonate-based additives with a substitution group selected from
halogens, a cyano (CN), or a nitro (NO.sub.2), and additives such
as vinylene carbonate, divinylsulfone, or ethylene sulfite. The
additives help to improve the battery performance such as through
inhibition of high-temperature swelling, and by increasing
capacity, cycle life, and low-temperature characteristics. The
carbonate-based additive is preferably an ethylene carbonate
derivative represented by the following formula 5, and is more
preferably fluoroethylene carbonate.
##STR00001## where X is selected from the group consisting of
halogens, a cyano (CN) or a nitro (NO.sub.2).
The amount of the carbonate-based additive is from 0.01 to 10 parts
by weight based on 100 parts by weight of the total weight of the
electrolyte, and preferably from 0.01 to 5 parts by weight. A
carbonate-based additive of less than 0.01 parts by weight cannot
effectively suppress gas generation, and that of more than 10 parts
by weight deteriorates high-temperature cycle life characteristics
and causes swelling to occur.
The lithium salt acts as a source for supplying lithium ions in the
battery, and helps the working of the battery. Examples of suitable
lithium salts are LiPF.sub.6, LiBF.sub.4, LiSbF.sub.6, LiAsF.sub.6,
LiClO.sub.4, LiCF.sub.3SO.sub.3, LiN(CF.sub.3SO.sub.2).sub.2,
LiN(C.sub.2F.sub.5SO.sub.2).sub.2, LiAlO.sub.4, LiAlCl.sub.4,
LiN(C.sub.xF.sub.2x+1SO.sub.2)(Cy.sub.F2+1SO.sub.2) where x and y
are natural numbers, LiSO.sub.3CF.sub.3, and mixtures thereof.
The concentration of the lithium salt is from 0.6 to 2.0M, and
preferably from 0.7 to 1.6M. If the concentration of the lithium
salt is less than 0.6M, the viscosity of the electrolyte decreases,
thereby deteriorating electrolyte performance. If the concentration
of the lithium salt if more than 2.0M, the viscosity increases,
thereby reducing transfer of lithium ions.
The electrolyte of the present invention is present in the form of
liquid electrolyte, or as a solid polymeric electrolyte. The solid
polymeric electrolyte is obtained from a composition for preparing
a polymer electrolyte by addition of monomer and a polymeric
initiator to the liquid electrolyte, i.e. electrolytic
solution.
The monomer preferably includes a mixture of a first monomer having
at least two functional groups with an unsaturated bond represented
by formulas 2, 3, or 4 at a terminal end and having a molecular
weight of 50 to 100,000, or a mixture of the first monomer and a
second monomer having at least one functional group represented by
formulas 2, 3, or 4 and having a molecular weight of 50 to 100,000.
(R.sub.1)(R.sub.2)C.dbd.C(R.sub.3)--C(.dbd.O)-- (2)
(R.sub.1)(R.sub.2)C.dbd.C(R.sub.3)-- (3)
(R.sub.1)(R.sub.2)C.dbd.C(R.sub.3)--CH.sub.2-- (4) where, R.sub.1,
R.sub.2 and R.sub.3 are the same or are independently selected from
H, a C.sub.2 to C.sub.10 aliphatic or aromatic hydrocarbon,
--C.ident.N, or --OR.sub.5, where R.sub.5 is H, CH.sub.3,
C.sub.2H.sub.5, --F, --Cl or --Br.
The monomer is preferably present in an amount from 0.01 to 20 wt %
in the composition, and more preferably from 0.1 to 10 wt %. An
amount of less than 0.01 wt % of the monomer causes an extreme
swelling phenomenon, and an amount of more than 20 wt % causes
deteriorated battery performance.
Examples of the monomer include poly(ethylene
glycol)di(meth)acrylate, poly(propylene glycol)di(meth)acrylate,
polyesterpolyol di(methacrylate), polycarbonatepolyol diacrylate,
polycaprolactonediol di(meth)acrylate, trimethylolpropane
ethoxylated tri(meth)acrylate, trimethylolpropane propooxylated
tri(meth)acrylate, trimethylolpropane caprolactonated
tri(meth)acrylate, tetramethylolpropane ethoxylated
tri(meth)acrylate, tetramethylolpropane propooxylated
tri(meth)acrylate, tetramethylolpropane caprolactonated
tri(meth)acrylate, ditrimethylolpropane ethoxylated
tri(meth)acrylate, ditrimethylolpropane propoxylated
tri(meth)acrylate, ditrimethylolpropane caprolactonated
tri(meth)acrylate, dipentaerythritol ethoxylated di(meth)acrylate,
dipentaerythritol propoxylated di(meth)acrylate, dipentaerythritol
caprolactonated di(meth)acrylate, glycerol ethoxylated
di(meth)acrylate, glycerol propoxylated di(meth)acrylate, and
dipentaerythritol caprolactonated hexacrylate. Alternatively, the
monomer may be a monomer with vinyl group, allyl group or
vinylsulfone group at a terminal site thereof, or urethane
(meth)acrylate monomer.
The polymerization initiator may be one that can initiate
polymerization of the monomer and does not cause deterioration of
the battery performance. Exemplary are at least one selected from
organic peroxides and azo-based compounds. The organic peroxides
may be peroxydicarbonates such as
di(4-t-butylcyclohexyl)peroxydicarbonate, di-2-ethylhexyl peroxy
dicarbonate, di-isopropyl peroxydicarbonate, di-3-methoxy butyl
peroxy dicarbonate, t-butyl peroxy isopropyl carbonate, t-butyl
peroxy 2-ethylhexyl carbonate, 1,6-bis(t-butyl
peroxycarbonyloxy)hexane, or diethylene glycol-bis(t-butyl peroxy
carbonate); diacyl peroxides such as diacetyl peroxide, dibenzoyl
peroxide, dilauroyl peroxide, bis-3,5,5-trimethyl hexanoyl
peroxide; or peroxy esters such as t-butyl peroxy pivalate, t-amyl
peroxy pivalate, t-butyl peroxy-2-ethyl hexanoate, t-hexylperoxy
pivalate, t-butyl peroxy neodecanoate, t-butyl peroxy
neoheptanoate, t-hexylperoxy pivalate, 1,1,3,3-tetramethylbutyl
peroxy neodecarbonate, 1,1,3,3-tetramethyl butyl 2-ethylhexanoate,
t-amyl peroxy 2-ethyl hexanoate, t-butyl peroxy isobutyrate,
t-amylperoxy 3,5,5-trimethyl hexanoyl, t-butyl peroxy
3,5,5-trimethyl hexanoate, t-butyl peroxy acetate, t-butyl peroxy
benzoate, or di-butylperoxy trimethyl adipate. The azo-based
compound may be 2,2'-azo-bis(2,4-dimethylvaleronitrile) or
1,1'-azo-bis(cyanocyclo-hexane).
The polymerization initiator is present in an amount sufficient to
initiate polymerization of the monomer, and is suitably present in
an amount from 0.01 to 5 wt %.
A polymer electrolyte may be produced by using the polymer
electrolyte composition as in the following various procedures. One
method is that the polymer electrolyte composition is injected into
a battery case such as a metal can or a pouch in which a positive
electrode, a separator, and a negative electrode are placed, which
is then heated at 40 to 100.degree. C. for 30 minutes to 8 hours,
thereby hardening (polymerizing) the polymer electrolyte
composition to produce the polymer electrolyte. Another method is
that the polymer electrolyte composition is coated on a positive or
a negative electrode, and heat, ultraviolet rays, or electron beams
are irradiated into the electrode to coat the polymer electrolyte
on the surface of the positive or the negative electrode. The
produced electrode is inserted into a battery case and sealed to
fabricate a battery. A separator may be additionally used, or
alternatively the polymer electrolyte also acts as the separator,
so the separator may be not used.
A rechargeable lithium battery including the electrolyte of the
present invention includes a positive electrode and a negative
electrode.
The positive electrode includes a positive active material in which
lithium intercalation reversibly occurs. Examples of positive
active material are lithiated intercalation compounds and
preferably a nickel-based lithiated intercalation compound because
of its higher capacity. More preferably, in order to achieve high
capacity and other battery performance improvements, a mixture of
the nickel-based lithiated intercalation compound and a
cobalt-based compound or manganese-based compound is used.
The swelling phenomenon especially occurs because of the
nickel-based compound, so the effect of using the electrolyte of
the present invention can be maximized when a nickel-based compound
is used. The nickel-based compound may be one selected from the
group consisting of compounds represented by formulas 6 and 7.
Li.sub.xNi.sub.yM.sub.1-yA.sub.2 (6)
Li.sub.xNi.sub.yM.sub.1-yO.sub.2-zX.sub.z (7) where
0.90.ltoreq.x.ltoreq.1.1, 0.1.ltoreq.y.ltoreq.0.9, and
0.ltoreq.z.ltoreq.0.5; M is at least one selected from Al, Ni, Co,
Mn, Cr, Fe, Mg, Sr, V, and rare earth elements; A is selected from
O, F, S, and P; and X is F, S, or P.
The cobalt-based or the manganese-based compound is any one used as
an active material, and examples include those selected from the
group consisting of compounds represented by formulas 8 to 12.
Li.sub.xMn.sub.1-yM.sub.yA.sub.2 (8)
Li.sub.xMn.sub.1-yM.sub.yO.sub.2-zX.sub.z (9)
Li.sub.xMn.sub.2O.sub.4-zX.sub.z (10)
Li.sub.xCo.sub.1-yM.sub.yA.sub.2 (11)
Li.sub.xCo.sub.1-yM.sub.yO.sub.2-zX.sub.z (12) where
0.90.ltoreq.x.ltoreq.1.1, 0.ltoreq.y.ltoreq.0.5,
0.ltoreq.z.ltoreq.0.5, and 0.ltoreq..alpha..ltoreq.2; M is at least
one selected from the group consisting of Al, Ni, Co, Mn, Cr, Fe,
Mg, Sr, V, and a earth elements; A is selected from O, F, S, and P,
and X is F, S, or P.
The negative electrode includes a negative active material in which
lithium intercalation reversibly occurs and examples are
crystalline or amorphous carbon, or carbon composites.
The positive and the negative electrode are respectively produced
by mixing the active material, a conductive agent, and a binder in
a solvent to prepare an active material composition, and coating
the composition on a current collector. The electrode preparation
is well known in the related art, and is easily understood by one
of ordinary skill in the art.
The conductive agent includes any conventional conductive agent
used for an active material composition as long as it is chemically
inert and has electrical conductivity. Examples thereof are one or
a mixture selected from natural graphite, artificial graphite,
carbon black, acetylene black, ketjen black; carbon fiber, and
metal fibers such as copper, nickel, aluminum, and silver.
The binder includes any conventional binder used for an active
material composition as long as it firmly adheres to the active
material and the conductive agent on the current collector, and the
binder may be styrene-butadiene rubber, polyvinyl alcohol,
carboxymethylcellulose, hydroxylpropylenecellulose,
diacetylenecellulose, polyvinylchloride, polyvinylpyrrolidone,
polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, or
polypropylene. Most preferred are styrene-butadiene rubber
compounds.
The solvent includes any conventional solvent used for an active
material composition as long as it sufficiently distributes the
active material, the conductive agent, and the binder. Examples of
the solvent include be N-methyl pyrrolidone.
One embodiment of the lithium rechargeable battery according to the
present invention is shown in FIG. 1. The rechargeable lithium
battery 1 includes a positive electrode 3; a negative electrode 2;
a separator 4 interposed between the positive electrode 3 and the
negative electrode 2; an electrolyte in which the positive
electrode 2, the negative electrode 3, and the separator 4 are
immersed; a cylindrical battery case 5; and a sealing portion 6.
The configuration of the rechargeable lithium battery is not
limited to the structure shown in FIG. 1, as it can be readily
modified into a prismatic or pouch type battery as is well
understood in the related art.
The positive electrode includes a positive active material in which
lithium intercalation reversibly occurs. Examples of positive
active materials are lithium transition metal oxides such as
LiCoO.sub.2, LiNiO.sub.2, LiMnO.sub.2, LiMn.sub.2O.sub.4, or
LiNi.sub.1-x-yCo.sub.xM.sub.yO.sub.2 where 0.ltoreq.x.ltoreq.1,
0.ltoreq.y.ltoreq.1, 0.ltoreq.x+y.ltoreq.1, and M is metal such as
Al, Sr, Mg, or La.
The negative electrode includes a negative active material in which
lithium intercalation reversibly occurs. Examples of negative
active materials are crystalline or amorphous carbonaceous
material, or carbon composites.
The positive active material and the negative active material are
respectively coated on a current collector to produce electrodes,
and the electrodes are wound together with or laminated on a
separator to produce an electrode element. The electrode element is
inserted into a battery case such as a can, and an electrolyte is
injected into the case to fabricate a rechargeable lithium battery.
The separator may be resin such as polyethylene or
polypropylene.]
The following Examples further illustrate the present invention in
detail, but are not to be construed to limit the scope thereof.
Example 1
1.5M LiBF.sub.4 was dissolved in a mixed solvent of ethylene
carbonate, .gamma.-butyrolactone, and valeronitrile in the volume
ratio of 3:6:1 to prepare an electrolyte.
Using the electrolyte, a LiCoO.sub.2 positive electrode, and a
graphite negative electrode, a rechargeable lithium cell was
fabricated. The amount of the electrolyte was 2.2 g.
Example 2
1.5M LiBF.sub.4 was dissolved in a mixed solvent of ethylene
carbonate, .gamma.-butyrolactone, and heptanenitrile in the volume
ratio of 3:6:1 to prepare an electrolyte.
Using the electrolyte, a LiCoO.sub.2 positive electrode, and a
graphite negative electrode, a rechargeable lithium cell was
fabricated. The amount of the electrolyte was 2.2 g.
Example 3
1.5M LiBF.sub.4 was dissolved in a mixed solvent of ethylene
carbonate, .gamma.-butyrolactone, and capronitrile in the volume
ratio of 3:6:1 to prepare an electrolyte.
Using the electrolyte, a LiCoO.sub.2 positive electrode, and a
graphite negative electrode, a rechargeable lithium cell was
fabricated. The amount of the electrolyte was 2.2 g.
Example 4
1.15M LiPF.sub.6 was dissolved in a mixed solvent of ethylene
carbonate, .gamma.-butyrolactone, and valeronitrile in the volume
ratio of 3:6:1 to prepare an electrolyte.
Using the electrolyte, a LiCoO.sub.2 positive electrode, and a
graphite negative electrode, a rechargeable lithium cell was
fabricated. The amount of the electrolyte was 2.2 g.
Example 5
1.15M LiPF.sub.6 was dissolved in a mixed solvent of ethylene
carbonate, .gamma.-butyrolactone, and valeronitrile in the volume
ratio of 3:5:2 to prepare an electrolyte.
Using the electrolyte, a LiCoO.sub.2 positive electrode, and a
graphite negative electrode, a rechargeable lithium cell was
fabricated. The amount of the electrolyte was 2.2 g.
Example 6
1.15M LiPF.sub.6 was dissolved in a mixed solvent of ethylene
carbonate, .gamma.-butyrolactone, and valeronitrile in the volume
ratio of 3:5:2 to prepare an electrolyte.
Using the electrolyte, a LiCoO.sub.2 positive electrode, and a
graphite negative electrode, a rechargeable lithium cell was
fabricated. The amount of the electrolyte was 2.2 g.
Example 7
1.15M LiPF.sub.6 was dissolved in a mixed solvent of ethylene
carbonate, .gamma.-butyrolactone, and valeronitrile in the volume
ratio of 3:5:2 to prepare an electrolyte.
Using the electrolyte, a LiCoO.sub.2 positive electrode, and a
graphite negative electrode, a rechargeable lithium cell was
fabricated. The amount of the electrolyte was 2.2 g.
Example 8
1.15M LiPF.sub.6 was dissolved in a mixed solvent of ethylene
carbonate, ethylmethyl carbonate, and valeronitrile in the volume
ratio of 3:6:1 to prepare an electrolyte.
Using the electrolyte, a LiCoO.sub.2 positive electrode, and a
graphite negative electrode, a rechargeable lithium cell was
fabricated. The amount of the electrolyte was 2.2 g.
Example 9
1.15M LiPF.sub.6 was dissolved in a mixed solvent of ethylene
carbonate, dimethyl carbonate, and valeronitrile in the volume
ratio of 3:5:2 to prepare an electrolyte.
Using the electrolyte, a LiCoO.sub.2 positive electrode, and a
graphite negative electrode, a rechargeable lithium cell was
fabricated. The amount of the electrolyte was 2.2 g.
Example 10
1.15M LiPF.sub.6 was dissolved in a mixed solvent of ethylene
carbonate, diethyl carbonate, and valeronitrile in the volume ratio
of 3:6:1 to prepare an electrolyte.
Using the electrolyte, a LiCoO.sub.2 positive electrode, and a
graphite negative electrode, a rechargeable lithium cell was
fabricated. The amount of the electrolyte was 2.2 g.
Example 11
A rechargeable lithium cell was fabricated by the same procedure as
in Example 1, except that a positive active material was produced
by mixing LiNi.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2 with LiCoO.sub.2
at a weight ratio of 8:2, and the amount of the electrolyte was 2.1
g.
Example 12
A rechargeable lithium cell was fabricated by the same procedure as
in Example 2, except that a positive active material was produced
by mixing LiNi.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2 with LiCoO.sub.2
at a weight ratio of 8:2, and the amount of the electrolyte was 2.1
g.
Example 13
A rechargeable lithium cell was fabricated by the same procedure as
in Example 3, except that a positive active material was produced
by mixing LiNi.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2 with LiCoO.sub.2
at a weight ratio of 8:2, and the amount of the electrolyte was 2.1
g.
Example 14
A rechargeable lithium cell was fabricated by the same procedure as
in Example 4, except that a positive active material was produced
by mixing LiNi.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2 with LiCoO.sub.2
at a weight ratio of 8:2, and the amount of the electrolyte was 2.1
g.
Example 15
A rechargeable lithium cell was fabricated by the same procedure as
in Example 5, except that a positive active material was produced
by mixing LiNi.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2 with LiCoO.sub.2
at a weight ratio of 8:2, and the amount of the electrolyte was 2.1
g.
Example 16
A rechargeable lithium cell was fabricated by the same procedure as
in Example 6 except that a positive active material was produced by
mixing LiNi.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2 with LiCoO.sub.2 at
a weight ratio of 8:2, and the amount of the electrolyte was 2.1
g.
Example 17
A rechargeable lithium cell was fabricated by the same procedure as
in Example 11, except that an electrolyte was prepared by
dissolving 1.15M LiPF.sub.6 in a mixed solvent of ethylene
carbonate, diethyl carbonate, and valeronitrile at a volume ratio
of 3:5:2.
Example 18
A rechargeable lithium cell was fabricated by the same procedure as
in Example 11, except that an electrolyte was prepared by
dissolving 1.15M LiPF.sub.6 in a mixed solvent of ethylene
carbonate, diethyl carbonate and valeronitrile at a volume ratio of
30:55:15.
Example 19
A rechargeable lithium cell was fabricated by the same procedure as
in Example 1, except that a mixed lithium salt of LiPF.sub.6 and
LiBF.sub.4 at a weight ratio of 99.9:0.1 was used.
Example 20
A rechargeable lithium cell was fabricated by the same procedure as
in Example 7, except that a mixed lithium salt of LiPF.sub.6 and
LiBF.sub.4 at a weight ratio of 99.9:0.1 was used.
Comparative Example 1
A rechargeable lithium cell was fabricated by the same procedure as
in Example 1, except that an electrolyte was prepared by dissolving
1.15M LiPF.sub.6 in a mixed solvent of ethylene carbonate,
ethylmethyl carbonate, propylene carbonate, and fluorobenzene at a
volume ratio of 30:55:15.
Comparative Example 2
A rechargeable lithium cell was fabricated by the same procedure as
in Example 1, except that an electrolyte was prepared by dissolving
1.15M LiPF.sub.6 in a mixed solvent of ethylene carbonate,
ethylmethyl carbonate, and fluorobenzene at a volume ratio of
30:55:15.
Comparative Example 3
A rechargeable lithium cell was fabricated by the same procedure as
in Example 11, except that an electrolyte was prepared by
dissolving 1.5M LiBF.sub.4 in a mixed solvent of ethylene
carbonate, .gamma.-butyrolactone, and diethyl carbonate at a volume
ratio of 4:4:2.
Comparative Example 4
A rechargeable lithium cell was fabricated by the same procedure as
in Example 11, except that an electrolyte was prepared by
dissolving 1.5M LiBF.sub.4 in a mixed solvent of ethylene
carbonate, .gamma.-butyrolactone, and fluorobenzene at a volume
ratio of 30:55:15.
Comparative Example 5
A rechargeable lithium cell was fabricated by the same procedure as
in Example 11, except that an electrolyte was prepared by
dissolving 1.15M LiPF.sub.6 in a mixed solvent of ethylene
carbonate, ethylmethyl carbonate, propylene carbonate, and
fluorobenzene at a volume ratio of 30:55:5:10.
Comparative Example 6
A rechargeable lithium cell was fabricated by the same procedure as
in Example 11, except that an electrolyte was prepared by
dissolving 1.15M LiPF.sub.6 in a mixed solvent of ethylene
carbonate, ethylmethyl carbonate, and fluorobenzene at a volume
ratio of 3:6:1.
Comparative Example 7
A rechargeable lithium cell was fabricated by the same procedure as
in Example 11, except that an electrolyte was prepared by
dissolving 1.5M LiBF.sub.4 in a mixed solvent of ethylene
carbonate, .gamma.-butyrolactone, and diethyl carbonate at a volume
ratio of 4:4:2.
Comparative Example 8
A rechargeable lithium cell was fabricated by the same procedure as
in Example 11, except that an electrolyte was prepared by
dissolving 1.5M LiBF.sub.4 in a mixed solvent of ethylene
carbonate, .gamma.-butyrolactone, fluorobenzene, and diethyl
carbonate at a volume ratio of 3:5:1:1.
Comparative Example 9
A rechargeable lithium cell was fabricated by the same procedure as
in Example 11, except that an electrolyte was prepared by
dissolving 1.3M LiPF.sub.6 in a mixed solvent of ethylene
carbonate, ethylmethyl carbonate, propylene carbonate, and
fluorobenzene at a volume ratio of 30:55:5:15.
Comparative Example 10
A rechargeable lithium cell was fabricated by the same procedure as
in Example 11, except that an electrolyte was prepared by
dissolving 1.3M LiPF.sub.6 in a mixed solvent of ethylene
carbonate, and ethylmethyl carbonate at a volume ratio of 3:7.
The lithium cells according to Examples 1 to 12 and Comparative
Examples 1 to 8 were constant-current and constant-voltage charged
at a 0.5 C rate and a cut-off voltage of 4.2V and 20 mAh, and the
charged cells were allowed to stand in an oven of 85.degree. C. for
4 hours. Thereafter, the thicknesses of the cells were measured.
The increases in the thickness in comparison to the initial charged
cells are shown in Table 1.
TABLE-US-00001 TABLE 1 Increase in thickness (%) Example 1 1.1
Example 2 1.6 Example 3 1.1 Comparative Example 7 7.2 Comparative
Example 8 6.2 Example 4 7 Example 5 6 Example 6 6 Example 7 7
Example 8 9 Example 9 1.5 Example 10 2.3 Comparative Example 5 95.1
Comparative Example 6 120 Example 11 4.9 Example 12 5.6 Example 13
5.5 Comparative Example 3 3.5 Comparative Example 4 3.8 Example 14
12.7 Example 15 10.4 Example 16 10.0 Example 19 1.1 Example 20 3.5
Example 17 20 Example 18 30 Comparative Example 9 120 Comparative
Example 10 86 Comparative Example 1 30 Comparative Example 2 33
It is evident from Table 1 that the increase in thickness of the
cells according to Examples 1 to 20 was reduced compared to those
of the cells according to Comparative Example 1 to 10. These
results indicate that swelling was suppressed in the cells
according to Examples 1 to 20 compared with Comparative Examples 1
to 10. In particular, the increases in thickness of the cells
according to Examples 4 and 5 were substantially reduced in
comparison to Comparative Example 1 and 2, even though the cells
according to Examples 4 and 5 and Comparative Examples 1 and 2
included ethylene carbonate and ethylmethyl carbonate.
The cells according to Examples 7 to 10 and Comparative Example 1
were charged under constant current and constant voltage at a 1 C
rate and a cut-off voltage of 4.2V and 0.1 C (82 mAh), and
discharged at constant current to a cut-off voltage of 3V. The
cycle life characteristics were measured and the results are shown
in FIG. 2. As shown in FIG. 2, the cells according to Examples 7 to
10 exhibited cycle life characteristics corresponding to that of
Comparative Example 1. Thus, the electrolyte of the present
invention can effectively improve storage characteristics and
suppress swell at high temperatures without deterioration of
battery performance in areas such as in capacity, high-rate,
low-temperature, and cycle life characteristics.
Example 21
1.5 wt % of a Dipentaerythritol caprolactonated hexaacrylate
monomer (Nippon Kayaku) and di(4-t-butylcyalohexyl
peroxydicarbonate) ("Perkadox 16", AKZO NOBEL) were added to 98.5
wt % of an electrolytic solution of 1.3M LiPF.sub.6 in ethylene
carbonate, diethyl carbonate, and valeronitrile (3:5:2 volume
ratio) and then mixed for 10 minutes to prepare a composition for
preparing a polymer electrolyte. At this time, the amount of the
initiator was 5 wt % based on the amount of the monomer.
The positive electrode included a mixed positive active material of
LiNi.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2 and LiCoO.sub.2 at a weight
ratio of 6:4, a carbon black conduct agent, and a polyvinylidene
fluoride binder and the negative electrode included a natural
graphite negative active material and a styrene-butadiene rubber
binder. The positive electrode, the negative electrode and a
separator were wound to produce a jelly-roll, and the jelly-roll
was inserted in to an Al pouch case and partially sealed. The
composition was injected into the case and it was completely
sealed. The amount of the composition was 2.62 g. The sealed case
was allowed to stand at 70.degree. C. for 4 hours to fabricate a
rechargeable lithium cell with a gel polymer electrolyte.
Example 22
A rechargeable lithium cell was fabricated by the same procedure as
in Example 21, except that heptane nitrile was used instead of
valeronitrile.
Example 23
A rechargeable lithium cell was fabricated by the same procedure as
in Example 21, except that caprilonitrile was used instead of
valeronitrile.
Example 24
A rechargeable lithium cell was fabricated by the same procedure as
in Example 21, except that cyclohexane carbonitrile was used
instead of valeronitrile.
Example 25
A rechargeable lithium cell was fabricated by the same procedure as
in Example 21, except that 2-fluorobenzonitrilee was used instead
of valeronitrile.
Example 26
A rechargeable lithium cell was fabricated by the same procedure as
in Example 21 except that a mixed solution of 1.3M LiPF.sub.6 in
ethylene carbonate, diethyl carbonate, and valeronitrile at a
volume ratio of 30:65:5 was used as an electrolytic solution.
Example 27
A rechargeable lithium cell was fabricated by the same procedure as
in Example 21, except that a mixed solution of 1.3M LiPF.sub.6 in
ethylene carbonate, diethyl carbonate, and valeronitrile at a
volume ratio of 30:40:30 was used as an electrolytic solution.
Example 28
A rechargeable lithium cell was fabricated by the same procedure as
in Example 21, except that a mixed solution of 1.3M LiPF.sub.6 in
ethylene carbonate, diethyl carbonate, and valeronitrile at a
volume ratio of 30:55:15 was used as an electrolytic solution.
Example 29
A rechargeable lithium cell was fabricated by the same procedure as
in Example 21, except that a mixed solution of 1.3M LiPF.sub.6 in
ethylene carbonate, diethyl carbonate, and valeronitrile at a
volume ratio of 30:45:25 was used as an electrolytic solution.
Example 30
A rechargeable lithium cell was fabricated by the same procedure as
in Example 21, except that a mixed solution of 1.3M LiPF.sub.6 in
ethylene carbonate, diethyl carbonate, and valeronitrile at a
volume ratio of 15:65:20 was used as an electrolytic solution.
Example 31
A rechargeable lithium cell was fabricated by the same procedure as
in Example 21, except that a mixed solution of 1.3M LiPF.sub.6 in
ethylene carbonate, .gamma.-butyrolactone, and valeronitrile at a
volume ratio of 30:50:20 was used as an electrolytic solution.
Example 32
A rechargeable lithium cell was fabricated by the same procedure as
in Example 21, except that a mixed solution of 1.3M LiPF.sub.6 in
ethylene carbonate, .gamma.-butyrolactone, and valeronitrile at a
volume ratio of 15:65:20 was used as an electrolytic solution.
Example 33
A rechargeable lithium cell was fabricated by the same procedure as
in Example 21, except that fluoroethylene carbonate was added to
the electrolytic solution in an amount of 3% based on the
electrolytic solution.
Example 34
A rechargeable lithium cell was fabricated by the same procedure as
in Example 21, except that a mixed solution of 1.3M LiPF.sub.6 in
ethylene carbonate, .gamma.-butyrolactone, diethyl carbonate, and
valeronitrile at a volume ratio of 15:40:30:15 was used as an
electrolytic solution.
Comparative Example 10
A rechargeable lithium cell was fabricated by the same procedure as
in Example 21, except that a mixed solution of 1.3M LiPF.sub.6 in
ethylene carbonate, ethylmethyl carbonate, propylene carbonate, and
fluorobenzene at a volume ratio of 30:55:5:10 was used as an
electrolytic solution.
Comparative Example 11
A rechargeable lithium cell was fabricated by the same procedure as
in Example 21, except that poly(ethylene glycol)dimethacrylate was
used as a compound for forming a polymer.
Comparative Example 12
A rechargeable lithium cell was fabricated by the same procedure as
in Example 21, except that a mixed solution of 1.3M LiPF.sub.6 in
acetonitrile and ethylene carbonate at a volume ratio of 7:3 was
used as an electrolytic solution.
Comparative Example 13
A rechargeable lithium cell was fabricated by the same procedure as
in Example 21, except that a mixed solution of 1.3M LiPF.sub.6 in
acetonitrile and ethylene carbonate at a volume ratio of 1:1 was
used as an electrolytic solution.
Comparative Example 14
A rechargeable lithium cell was fabricated by the same procedure as
in Example 21, except that a mixed solution of 1.3 LiPF.sub.6 in
acetonitrile, ethylene carbonate, and diethyl carbonate at a volume
ratio of 40:30:30 was used as an electrolytic solution.
Example 35
A rechargeable lithium cell was fabricated by the same procedure as
in Example 21, except that a mixed positive active material of
LiNi.sub.0.8Co.sub.0.15Mn.sub.0.05O.sub.2 and LiCoO.sub.2 was used
as a positive active material.
Example 36
A rechargeable lithium cell was fabricated by the same procedure as
in Example 21 except that a mixed positive active material of
LiNi.sub.0.75Co.sub.0.2Mn.sub.0.05O.sub.2 and LiCoO.sub.2 was used
as a positive active material.
Capacity Test
The cells according to Examples 21 to 36 and Comparative Examples
10 to 14 were constant-current and constant-voltage charged at 0.5
C to 4.2V and a cut-off time of 3 hours, and constant-current
discharged at 0.2 C and a cut-off voltage of 2.75V. The capacity
was measured and the results are presented in Table 2.
Swelling Characteristics
The cells according to Examples 21 to 36 and Comparative Examples
10 to 16 were constant-current charge and constant-voltage charged
at 0.5 C to 4.2V and a cut-off condition of 0.1 C. The charged
cells were allowed to stand at 85.degree. C. in a hot-wind oven for
4 hours, and the thicknesses thereof were measured. The increase in
thickness compared to the initial charged cell for each was
measured and the results are presented in Table 2.
Cycle Life Characteristics
The cells according to Examples 21 to 36 and Comparative Examples
10 to 14 were charged 500 times at 1 C, and the cycle life
characteristics (retention capacity %) were measured. The results
are shown in Table 2.
TABLE-US-00002 TABLE 2 Cycle life (retention Capacity capacity %
for Increase in (mAh) 500 times) thickness (%) Example 21 920 90
1.5 Example 22 918 88 2.0 Example 23 921 88 1.8 Example 24 920 89
2.1 Example 25 920 87 2.3 Example 26 921 92 3.5 Example 27 918 80
1.0 Example 28 919 89 1.5 Example 29 917 85 1.0 Example 30 921 88
2.3 Example 31 918 88 1.9 Example 32 920 85 2.0 Example 33 919 92
3.5 Example 34 919 87 1.8 Example 35 920 89 1.7 Example 36 916 90
3.4 Comparative Example 10 922 92 44.9 Comparative Example 11 890
60 12 Comparative Example 12 900 80 23 Comparative Example 13 911
74 32 Comparative Example 14 917 82 19
As shown in Table 2, the cells according to Examples 21 to 36
exhibited corresponding capacities to those according to
Comparative Examples 10 to 14, but exhibited good cycle life
characteristics, and excellent swelling inhibition. Hence, the
cells according to Examples 21 to 35 exhibit improved safety while
the capacity and the cycle life characteristics are maintained.
Example 37
1.15M LiPF.sub.6 was dissolved in a mixed solution of ethylene
carbonate, diethyl carbonate and valeronitrile at a volume ratio of
30:50:20 to prepare an electrolyte.
The positive electrode included a mixed positive active material of
LiNi.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2 and LiCoO.sub.2 at a weight
ratio of 6:4, a carbon black conductive agent, and a polyvinylidene
fluoride binder, and the negative electrode included a natural
graphite negative active material and a styrene-butadiene rubber
binder. Using the positive electrode, the negative electrode, and
the electrolyte, a lithium cell was fabricated.
Example 38
A lithium cell was fabricated by the same procedure as in Example
37, except that heptane nitrile was used instead of
valeronitrile.
Example 39
A lithium cell was fabricated by the same procedure as in Example
37, except that caprilonitrile was used instead of
valeronitrile.
Example 40
A lithium cell was fabricated by the same procedure as in Example
37, except that cyclohexane carbonitrile was used instead of
valeronitrile.
Example 41
A lithium cell was fabricated by the same procedure as in Example
37, except that 2-fluorobenzonitirlee was used instead of
valeronitrile.
Example 42
A lithium cell was fabricated by the same procedure as in Example
37, except that 1.15M LiPF.sub.6 was dissolved in a mixed solution
of ethylene carbonate, diethyl carbonate, and valeronitrile at a
volume ratio of 30:40:30 to prepare an electrolyte.
Example 43
A lithium cell was fabricated by the same procedure as in Example
37, except that 1.15M LiPF.sub.6 was dissolved in a mixed solution
of ethylene carbonate, diethyl carbonate, and valeronitrile at a
volume ratio of 30:55:15 to prepare an electrolyte.
Example 44
A lithium cell was fabricated by the same procedure as in Example
37, except that 1.15M LiPF.sub.6 was dissolved in a mixed solution
of ethylene carbonate, diethyl carbonate, and valeronitrile at a
volume ratio of 30:45:25 to prepare an electrolyte.
Comparative Example 15
A lithium cell was fabricated by the same procedure as in Example
37, except that 1.15M LiPF.sub.6 was dissolved in a mixed solution
of ethylene carbonate, ethylmethyl carbonate, propylene carbonate,
and fluorobenzene at a volume ratio of 30:55:10 to prepare an
electrolyte.
Comparative Example 16
A lithium cell was fabricated by the same procedure as in Example
37, except that 1.15M LiPF.sub.6 was dissolved in a mixed solution
of acetonitrile and ethylene carbonate at a volume ratio of 7:3 to
prepare an electrolyte.
Comparative Example 17
A lithium cell was fabricated by the same procedure as in Example
37, except that 1.15M LiPF.sub.6 was dissolved in a mixed solution
of acetonitrile and ethylene carbonate at a volume ratio of 1:1 to
prepare an electrolyte.
Comparative Example 18
A lithium cell was fabricated by the same procedure as in Example
37, except that 1.15M LiPF.sub.6 was dissolved in a mixed solution
of acetonitrile, ethylene carbonate, and diethyl carbonate at a
volume ratio of 40:30:30 to prepare an electrolyte.
Capacity, cycle life characteristics and swelling characteristics
tests were performed on the cells according to Examples 37 to 44
and Comparative Examples 16 to 19. The results are presented in
Table 3.
TABLE-US-00003 TABLE 3 Cycle life (retention capacity % for
Increases in Capacity (mAh) 500 times) thickness (%) Example 37 923
89 15.4 Example 38 921 88 16.2 Example 39 922 88 14.9 Example 40
921 87 14.5 Example 41 923 90 17.6 Example 42 919 83 12.1 Example
43 924 89 15.0 Example 44 920 85 12.2 Comparative 925 92 105
Example 16 Comparative 900 80 26 Example 17 Comparative 910 83 30.1
Example 18 Comparative 920 88 27.5 Example 19
Example 45
1 wt % of a Dipentaerythritol caprolactonated hexacrylate
derivative monomer (Nippon Kayaku) and a di(4-t-butylcyalohexyl
peroxydicarbonate ("Perkadox 16", AKZO NOBEL) were added to 98.5 wt
% of an electrolytic solution of 1.3M LiPF.sub.6 in ethylene
carbonate, .gamma.-butyrolactone, diethyl carbonate, and
valeronitrile (15:55:20:10 volume ratio) and then mixed for 10
minutes to prepare a composition for preparing a polymer
electrolyte. At this time, the amount of the initiator was 3 wt %
based on the amount of the monomer.
The positive electrode included a LiCoO.sub.2 positive active
material, a carbon black conductive agent, and a polyvinylidene
fluoride binder, and the negative electrode included a natural
graphite negative active material and a styrene-butadiene rubber
binder. The positive electrode, the negative electrode, and a
separator were wound to produce a jelly-roll, and the jelly-roll
was inserted in to an Al pouch case and partially sealed. The
composition was injected into the case and was completely sealed.
The amount of the composition was 2.62 g. The sealed case was
allowed to stand at 70.degree. C. for 4 hours to fabricate a
rechargeable lithium cell with a gel polymer electrolyte.
Overdischarge Test
The capacity recovery step was performed on the cell according to
Example 45. The capacity recovery step included a first step
including charging at 500 mA to 4.2V under a cut-off condition of
50 mA, a first discharging at 300 mA and a cut-off voltage of
3.00V, a second discharging at 2 mA and a cut-off voltage of 2.75V,
and a third discharging at 1 mA, and a cut-off voltage of 0.00V,
and allowing to stand for 60 minutes; and then a second step
including a first charging at 500 mA and a cut-off voltage of 3V, a
second charging at 500 mA and 4.2V under a cut-off condition of 50
mA, and then discharging at 300 mA to a cut-off voltage of 3V.
The capacity recovery step was referred to as 1 cycle, and it was
repeated three times. The initial capacity and the discharge
capacity for each cycle were measured and then the recovery
capacity percentage was obtained from the capacity after each cycle
with respect to the initial capacity. The initial capacity was a
capacity after the cell was charged at 500 mA and 4.2V under a
cut-off condition of 50 mA, and first discharged at 300 mA under a
cut-off voltage of 3.0V. The measured initial capacity was 895 mAh.
When the initial capacity of 895 mAh was 100%, a capacity at 1
cycle was 834 mAh, that is, 97%, at 2 cycles, 832 mAh, 97%, and at
3 cycles, 839 mAh, 98%. These results indicate good capacity
recovery.
While the present invention has been described in detail with
reference to the preferred embodiments, those skilled in the art
will appreciate that various modifications and substitutions can be
made thereto without departing from the spirit and scope of the
present invention as set forth in the appended claims.
* * * * *